<p>A series of new transition metal Schiff base complexes was synthesized via the reaction of H<sub>2</sub>L (N,N′-bis(naphthylidene)-2-aminobenzylamine) with the transition metals (Cu<sup>2+</sup>, Co<sup>2+</sup>, Ni<sup>2+</sup>, Zn<sup>2+</sup> and Mn<sup>2+</sup>) and characterized by elemental analysis, <sup>1</sup>HNMR, FT-IR, UV-Vis spectroscopy, thermogravimetric analysis(TG) and in selected cases by X-ray crystallography. Thermodynamics of complex formation, electrochemistry of the metal Schiff base complexes and kinetic aspects of thermal decomposition of the complexes were also studied. The obtained formation constants change according to the following trend due to the electronegativity and Jahn-Teller effects of the central transition metals: Cu > Co > Ni > Zn >Mn. Cyclic voltammogram of the complexes in acetonitrile was done to evaluate the redox behavior of the complexes. Electrochemistry of these complexes showed a redox reaction without any successive reactions. Furthermore, kinetic parameters which calculated by Coats–Redfern equation revealed a first-order kinetics of thermal decomposition in all stages.</p>